JPH0721054B2 - Production of aromatic sulfide / sulfone polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the preparation of aromatic sulfide / sulfone polymers. In another aspect, the present invention relates to the preparation of aromatic sulfide / sulfone polymers that exhibit improved melt flow stability. In yet another aspect, the invention relates to producing aromatic sulfides / sulfones in a simplified and easily controlled manner.

Thermoplastic polymers with a high degree of heat resistance or thermal stability have been the subject of intense research and development by many laboratories around the world. Since thermoplastics composed of these polymers can be quickly and efficiently molded into articles with simple or complex designs, mass production techniques have been utilized to provide a wide variety of useful products. As described above, the heat-resistant thermoplastic polymer has an important advantage that it can be used for applications such as electric appliance parts, electric wire coatings, automobile parts, and aircraft parts. Such polymers can often be used in the form of composites containing highly heat resistant fibers and fillers.

However, in order to be more widely used in such applications, thermoplastic polymers have excellent melt stability, that is, they withstand the high temperatures encountered during the molding operation, and do not undergo undue deterioration and / or premature curing. Must be done.

Arylene sulfide / sulfone polymers are known in the art, and methods for making these polymers are described in various U.S. Pat. No. 4,016,145, R. W. Campbell, 4,127,713.
No. 4,301,274.
While these patents have made significant and valuable advances to the art, there is a desire for a simpler process that can provide aromatic sulfide / sulfone polymers with high molecular weight as well as good melt flow properties.

Accordingly, one object of the present invention is to produce aromatic sulfide / sulfone polymers that exhibit high molecular weight.

Another object of the present invention is to provide a process for making high molecular weight aromatic sulfide / sulfone polymers that exhibit improved melt flow stability.

It is yet another object of the present invention to provide a simpler, more controllable process for making high molecular weight aromatic sulfide / sulfone polymers that exhibit improved melt flow stability.

Other objects and aspects of the invention, as well as some advantages, will be apparent from a study of this specification and the appended claims.

Briefly, the use of alkali metal carbonates or alkali metal carbonates plus alkali metal hydroxides in the preparation of aromatic sulfide / sulfone polymers results in the formation of high molecular weight, heat stable polymers. It has been found that the use of alkali metal carboxylates in the polymerization stage can be omitted and the post-treatment step of blocking the end groups of molecules can be omitted.

According to the invention, in effect the following components: (1) at least one dihaloaromatic sulfone, (2) at least one organic amide, (3) at least one alkali metal hydrosulfide, (4) water and (5) At least one member selected from the following groups, that is, a mixture of (a) an alkali metal carbonate, (b) an alkali metal carbonate and an alkali metal hydroxide (provided that the above mixture is used to form a target polymer). At least about 0.5 under sufficient temperature and time of polymerization conditions
Aromatic sulphide / in a process comprising contacting
A sulfone polymer is produced.

Thus, the present invention does not require an alkali metal carboxylate salt to promote the formation of high molecular weight polymers, and does not require an additional step of endcapping to promote melt flow stability of the polymers. At the same time, a method for producing an aromatic sulfide / sulfone polymer having excellent melt flow stability is provided.

The dihaloaromatic sulfone used in the method of the present invention can be represented by the following formula.

(In the formula, each X is selected from the group consisting of fluorine, chlorine, bromine and iodine, and Z is the following group: and A divalent radical selected from; m is 0 or 1; n is 0 or 1; A is selected from the group consisting of oxygen, sulfur, sulfonyl and CR ₂ ; and each R is hydrogen and 1 to about 4 Selected from the group consisting of alkyl radicals having 5 carbon atoms, the total number of carbon atoms in all R groups in the molecule is 0 to about 12. Preferably m is 0. ) Some examples of dihaloaromatic sulfones that can be used in the method of the present invention are bis (p-fluorophenyl) sulfone, bis (p-chlorophenyl) sulfone,
Bis (p-bromophenyl) sulfone, bis (p-iodophenyl) sulfone, p-chlorophenyl p-bromophenyl sulfone, p-iodophenyl 3-methyl-
4-fluorophenyl sulfone, bis (2-methyl-4)
-Chlorophenyl) sulfone, bis (2,5-diethyl-
4-Promophenyl) sulfone, bis (3-isopropyl-4-iodophenyl) sulfone, bis (2,5-dipropyl-4-chlorophenyl) sulfone, bis (2-butyl-4-fluorophenyl) sulfone, bis (2 , 3,5,6
-Tetramethyl-4-chlorophenyl) sulfone, 2-
Isobutyl-4-chlorophenyl 3-butyl-4-bromophenyl sulfone, 1,4-bis (p-chlorophenylsulfonyl) benzene, 1-methyl-2,4-bis (p
-Fluorophenylsulfonyl) benzene, 2,6-bis (p-bromophenylsulfonyl) naphthalene, 7-ethyl-1,5-bis (p-iodophenylsulfonyl) naphthalene, 4,4'-bis (p-chlorophenylsulfonyl) ) Biphenyl, bis [p- (p-bromophenylsulfonyl) phenyl] ether, bis [p- (p-chlorophenylsulfonyl) phenyl sulfide, bis [p
-(P-chlorophenylsulfonyl) phenyl] sulfone, bis [p- (p-bromophenylsulfonyl) -phenyl] methane, 5,5-bis [3-ethyl-4- (p-
Chlorophenylsulfonyl) phenyl] nonane, and the like and mixtures thereof. Bis (p-chlorophenyl) sulfone is preferred because of its ready availability and generally good results.

The organic amide used in the process of the present invention must be substantially liquid at the temperature and pressure of the reaction used. The amide may be cyclic or acyclic and may contain from 1 to about 10 carbon atoms per molecule.
Formamide, to name a few examples of suitable amides,
Acetamide, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-ethylpropionamide, N, N-dipropylbutyramide, 2
-Pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-2-pyrrolidone, ε-caprolactam, N-methyl-ε-caprolactam, N, N-ethylenedi-2-pyrrolidone, hexa There are methylphosphoramide, tetramethylurea, etc. and mixtures thereof. N-methyl-2-pyrrolidone is preferred due to its excellent results and ready availability.

Alkali metal hydrosulfides that can be used in accordance with the present invention include sodium hydrosulfide, lithium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide and mixtures thereof. Sodium hydrosulfide is preferable because it is easily available and good results are obtained. The alkali metal hydrosulfide can be conveniently used as an aqueous solution in the present invention. For example, an aqueous solution of NaSH containing about 60 weight percent NaSH is convenient to use.

Alkali metal carbonates that can be used in accordance with the present invention include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate and mixtures thereof. Sodium carbonate is preferred because it is easily available and generally good results are obtained.

According to the present invention, alkali metal hydroxides that can be used as a mixture with at least one alkali metal carbonate include lithium hydroxide, sodium hydroxide, potassium hydroxide,
There are rubidium hydroxide, cesium hydroxide and mixtures thereof. Sodium hydroxide is preferred because it is readily available and good results are obtained with this compound.

According to one aspect of the invention, if instead of at least one alkali metal carbonate alone, a mixture of at least one alkali metal carbonate and at least one alkali metal hydroxide is used, the mixture is at least about 0.
It should contain 5 mole percent alkali metal carbonate. Preferably the mixture will contain from about 5 to about 40 mole percent alkali metal carbonate, more preferably from about 15 to about 25 mole percent alkali metal carbonate.

The amount of alkali metal carbonate or the mixture of alkali metal carbonate and alkali metal hydroxide used according to the invention can be expressed in a molar ratio based on the alkali metal hydrosulfide. Thus, the molar ratio of alkali metal carbonate or alkali metal carbonate plus alkali metal hydroxide to alkali metal hydrosulfide is generally from about 1.1: 1 to about 1.
It is 0: 1 and preferably about 1.02: 1 to about 1.0: 1.

In yet another embodiment of the invention, the alkali metal carbonate is in situ in a mixture of compounds to be polymerized to produce an aromatic sulfide / sulfone polymer.
Includes making (on the fly). In this embodiment, for example carbon dioxide, preferably gaseous carbon dioxide, CO ₂
Is added to the mixture containing the alkali metal hydroxide present in an amount sufficient to react with and form an effective alkali metal carbonate under the conditions of appropriate temperature and pressure. Furthermore, according to this example, even if excess alkali metal hydroxide is present in the mixture that reacts with CO ₂ , the mixture of alkali metal carbonate and alkali metal hydroxide is then effective in situ. Will be generated. Those skilled in the art will appreciate the relative amounts of alkali metal hydroxide and CO ₂ to be used to provide the alkali metal carbonate or mixture thereof with alkali metal hydroxide to be generated in situ. Could be determined immediately.

The amount of dihaloaromatic sulfone used in accordance with the present invention can vary over a wide range, but generally the molar ratio of dihaloaromatic sulfone to alkali metal hydrosulfide is from about 0.9: 1 to about.
Good results are obtained at 1.2: 1. Preferably, this molar ratio is about 0.95: 1 to about 1.05: 1.

The amount of organic amide used in the present invention can also vary widely. Generally, the molar ratio of organic amide to alkali metal hydrosulfide is from about 4: 1 to about 16: 1, and preferably from about 6: 1 to about 1.
It will be 2: 1.

The amount of water used in the present invention can also vary widely, but generally good results are obtained when the molar ratio of water to organic amide is from about 0.2: 1 to about 2: 1. Preferably, this ratio is about 0.6:
It will be from 1 to about 1.2: 1.

The process of the present invention for producing aromatic sulfide / sulfone polymers is preferably carried out essentially with the following compounds: (1) at least one dihaloaromatic sulfone, (2) at least one organic amide. , (3)
At least one alkali metal hydrosulfide, (4) water, and (5) at least one member selected from the following group:
That is, a mixture of (a) an alkali metal carbonate, (b) an alkali metal carbonate and an alkali metal hydroxide, provided that the mixture contains at least about 0.5 mole percent alkali metal carbonate. The order of addition of the various compounds used in the method of the present invention can be altered if desired.

One convenient method is to charge all the compounds in any desired order into a suitable reaction vessel equipped with stirring means at about room temperature, then heat the mixture to the desired temperature with stirring and set to the desired temperature. When the temperature is reached, it is kept at that temperature for the desired time. It is also possible to preheat the mixture of only some compounds in a separate vessel and then add the previous mixture to the mixture of the remaining compounds preheated in the reaction vessel. In the above embodiments in which the alkali metal carbonate or a mixture thereof with an alkali metal hydroxide is prepared in situ, CO ₂ is preferably added to the mixture of compounds consisting of the alkali metal hydroxide.

The reaction temperature at which the polymerization is carried out can vary over a considerable range, but will generally be in the range of about 170 ° C to about 240 ° C, preferably in the range of about 185 ° C to about 225 ° C. The reaction time may vary widely depending in part on the reaction temperature, but will generally be in the range of about 0.5 hours to about 10 hours, preferably about 1 hour to about 4 hours. The pressure should be sufficient to keep the dihaloaromatic sulfone and organic amide substantially in the liquid phase.

Without wishing to be bound by any theory, the aromatic sulfide / sulfone polymer formed by the method of the invention described above is currently It is believed to have a repeating unit consisting of. However,
Each R, Z and m in the above formula is as previously defined.

The aromatic sulphide / sulphone polymer is produced in the form of particles in the process of the invention, so that the polymer is separated from the reaction mixture by conventional procedures, for example by collecting the reaction mixture by filtration and then washing it at least once with water. can do. A preferred recovery method is to dilute the hot reaction mixture with a mixture of water and organic amide and cool the cooled mixture with stirring. The separated polymer particles can then be washed with water, with at least a portion of the washing being carried out at an elevated temperature in the range of about 130 ° C to about 250 ° C to reduce ash-forming material and color. A polymer is obtained which is relatively clear and at the same time exhibits good melt flow stability under the conditions of melt processing operations such as injection molding.

The aromatic sulfide / sulfone polymer produced by the method of the present invention can be blended with fillers, fibers, pigments, extenders, other polymers and the like. The polymer gives a cured product with high thermal stability and good chemical resistance through crosslinking and / or chain extension, for example by heating at temperatures up to about 480 ° C in the presence of free oxygen-containing gases. Can be cured. These are useful in the production of coatings, films, moldings and fibers. The polymers show well-balanced properties for these applications, but the heat deflection temperature is especially outstanding.

Example 1 Poly (p-phenylene sulfide / sulfone) (PPS
To prepare S), a series of polymerization experiments were carried out in a 90-gallon reaction vessel equipped with a stirrer (500 rpm). The polymerization recipe for these experiments is as follows.

In each experiment, aqueous NaOH and a portion of NMP were placed in separate vessels.
Premix for 5 hours at ~ 125 ° C. Then, an aqueous NaSH solution was added, and the resulting mixture was left as it was for 30 minutes to obtain NaSH: NaOH:
An NMP complex was formed. Charge BCPS, a part of NMP, Na ₂ CO ₃ and, in some cases, NaOAc in a polymerization vessel to about 8
Heated to 8 ° C. The composite was then added to the polymerization vessel with successive NMP flushes. then
The reaction mixture was heated to 200 ° C. at a rate of 1.2 to 1.8 ° C./min over 58 to 90 minutes. Bring the reaction mixture to a temperature of 200 ° C.
Hold for 0 minutes.

At the end of the polymerization reaction, increase the speed of the stirrer to 550 rpm,
0.9-1.68 lb mol NMP and 2.78-5.93 lb mol water were added to the reactor. The reaction mixture is then 0.85-1.
The temperature was lowered at a rate of 2 ° C / min and cooled to 103 to 107 ° C. The resulting polymer slurry was filtered to facilitate recovery of NMP. The polymer was reslurried with deionized water (DI) in the room and filtered while rinsing with hot (82 ° C) DI. Polymer was then washed twice with degassed DI (176
℃) and filtered while rinsing with hot DI. The second hot washed slurry was treated with zinc acetate. The washing step used a slurry mixing tank and a nylon filter cloth on a moving horizontal belt filter to wash / rinse and separate the PPSS from the liquid. The washed PPSS from each experiment was dried and a portion of it sampled for internal viscosity testing. The results obtained are shown in Table I. The NMP / NaSH molar ratio was in the range of 6.17 to 6.20 unless otherwise specified. The BCPS / NaSH molar ratio is in the range of 0.9963 to 0.9989 and the H ₂ O / NMP molar ratio is in the range of 0.6 to 1.
The range was 4.

The internal viscosity of the PPSS sample is # 100 Canon-Fenske (Can
non-Fenske) normal type viscometer using N-methyl-2
-Pyrrolidone (NMP) as solvent with polymer concentration 0.5g / dl
Determined by NMP. Intrinsic viscosity provides a measure of the relative molecular weight of PPSS polymers of the same type.

The results in Table I show that the experiments carried out with a mixture of Na ₂ CO ₃ and NaOH produced polymers of at least as much acceptable molecular weight as those carried out in the absence of any alkali metal carbonate. ing. This is the same as for the polymerizations carried out with and without the presence of alkali metal carboxylates. Although the experiments carried out without alkali metal carboxylates give slightly lower molecular weights than the experiments carried out in the presence of alkali metal carboxylates, the polymer is still acceptable for molding applications.

Example II A series of polymerization experiments were carried out in a 1 gallon rapid stirred reactor to prepare PPSS. The polymerization recipe for these experiments is shown below.

In each experiment, the reaction vessel was charged with the above reactants and the reaction vessel was purged with N ₂ four times. The reaction mixture was heated to 200 ° C. and kept at that temperature for 3 hours. The reaction vessel is finally 10
A pressure of 0-175 psig was reached. At the end of the polymerization with 500 ml NMP
175-200 ml water was slowly charged to the reaction vessel.
The heating was stopped and the reaction mixture was slowly cooled with air through an internal cooling coil.

The reaction vessel was opened, and granular and fine PPSS was taken out from the inside. A 100 mesh screen was used to collect the granular polymer, rinsing once with acetone that was washed 3 times with water on the screen. The recovered polymer was charged into a reaction vessel with water, purged with N ₂ twice, and then washed with an aqueous solution of zinc acetate at high temperature (180 ° C.). The polymer was recovered, washed twice with water, rinsed with acetone and then dried in a vacuum oven at 200 ° C. for 6 hours. The results obtained are shown in Table II.

The results in Table II show that high quality PPSS is obtained using only a mixture of NaOH and Na ₂ CO ₃ without the addition of alkali metal carboxylates.
Is obtained.

Example III As an example of the present invention, several experiments were carried out to generate alkali metal carbonates in situ by adding CO ₂ to a reaction mixture consisting of alkali metal hydroxides.

In these experiments, a 1-gallon autoclave equipped with stirring means, heating means and cooling means (coil) was charged with the following substances.

Sodium hydrosulfide (NaSH) 1 gram mol Sodium hydroxide (NaOH) 1.246 〃 Bis (4-chlorophenyl) sulfone (BCPS) 1.00 〃
N-methyl-2-pyrrolidone (NMP) 8.00 〃 water 4.96 to 5.21 〃 NaSH was added as a 58.47 wt% aqueous solution, and NaOH was added as solid pellets. After charging the above mixture, the reactor was closed and purged with nitrogen gas three times.

Solid CO ₂ was then placed in a sample cylinder that was connected to the reactor and could withstand high pressure, and the contents of the cylinder were added to the reactor at the autogenous pressure generated by CO ₂ . The cylinder was then purged with nitrogen gas 2-3 times and pumped into the reactor.
The reactor was heated to 200 ° C and held for 3 hours. At this point the reactor pressure reached 150-175 psig. Next, when heating is over, add 500 ml of NMP and 200-250 ml of water to the reactor,
Air was blown through the internal coil to cool the reactor to room temperature.

The reactor was opened, and poly (phenylene sulfide / sulfone) PPSS in the form of particles and particles was taken out from the inside.
A 100 mesh screen was used to collect the particulate polymer, washed 3-4 times with water on the screen and rinsed with acetone. The microparticles were collected by filtration on a large Buchner funnel and similarly washed 3 times with water on the filter. The recovered polymer was placed in a vacuum oven at 200 ° C for 4
Dried for hours.

The results obtained in these experiments are shown in Table III below. Intrinsic viscosity (IV) is for a sample of particulate polymer.

The results presented in Table III show that the reaction mixture consisting of
We show that high-quality poly (phenylene sulfide / sulfone) can be produced by adding O ₂ and generating Na ₂ CO ₃ in situ. N compared to CO ₂ was added in these experiments
As aOH was always present in excess, CO ₂
The addition of resulted in a mixture of Na ₂ CO ₃ and NaOH.

Front Page Continuation (72) Inventor Affif Michael Nessewat 74006 Oklahoma, United States, Bartlesville, South East Kings Drive 1557, Apartment 1216 (72) Inventor Way-Tay Wade Shan Nagoya, Aichi Prefecture 32, Ibaraki-cho, Mizuho-ku, Yokohama (56) References JP-A-62-149725 (JP, A) JP-A-59-189125 (JP, A)

Claims (7)

[Claims] 1. A method for producing an aromatic sulfide / sulfone polymer, which comprises (1) at least one dihaloaromatic sulfone, (2) at least one organic amide, (3) at least one alkali metal hydrosulfide, (4) water, and (5) at least one of: (a) an alkali metal carbonate or (b) a mixture of an alkali metal carbonate and an alkali metal hydroxide, wherein the mixture is at least about 5 mole percent to about.
40 mole percent of alkali metal carbonate) is contacted under polymerization reaction conditions of temperature and time sufficient to form the polymer, and the alkali metal carbonate or the alkali metal carbonate in the mixture. The molar ratio of the sum of the alkali metal hydroxide to the alkali metal hydrosulfide is about 1.0: 1 to about 1.1: 1, and the molar ratio of the dihaloaromatic sulfone to the alkali metal hydrosulfide is about 0.9: 1 to about 1.2: 1, the molar ratio of the organic amide to the alkali metal hydrosulfide is about 4: 1 to about 16: 1, and the molar ratio of the water to the organic amide is about 0.6: 1 to. The method of making the aromatic sulfide / sulfone polymer, wherein the ratio of water to the alkali metal hydrosulfide is about 1.2: 1 and is at least about 2.4. 2. The method according to claim 5, wherein said (5) is a mixture of an alkali metal carbonate and an alkali metal hydroxide, and the molar percentage of the alkali metal carbonate in the mixture is about 15 to about 25. The method according to item 1. 3. The at least one dihaloaromatic sulfone is bis (4-chlorophenyl) sulfone, the at least one organic amide is N-methyl-2-pyrrolidone, and the at least one alkali metal hydrosulfide. Is sodium hydrosulfide, the alkali metal carbonate is sodium carbonate, and the alkali metal hydroxide is sodium hydroxide. 4. The method according to claim 1, wherein said (5) is an alkali metal carbonate. 5. The at least one dihaloaromatic sulfone is bis (4-chlorophenyl) sulfone, the at least one organic amide is N-methyl-2-pyrrolidone, and the at least one alkali metal hydrosulfide. Is sodium hydrosulfide and the alkali metal carbonate is sodium carbonate. 6. The mixture (5) is a mixture of an alkali metal carbonate and an alkali metal hydroxide, and the mixture contains the alkali metal hydroxide and carbon dioxide in situ. A process according to any one of claims 1 to 3, which is formed by contacting the mixture of 4) under conditions suitable to form the alkali metal carbonate. 7. The method of claim 6 wherein said carbon dioxide is added in gaseous form.